Classifications

• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
  • D02G3/48—Tyre cords
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
  • B60C15/0009—Tyre beads, e.g. ply turn-up or overlap features of the carcass terminal portion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0042—Reinforcements made of synthetic materials
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
  • D01G11/00—Disintegrating fibre-containing articles to obtain fibres for re-use
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
  • D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
  • D02G3/28—Doubled, plied, or cabled threads
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/02—Carcasses
  • B60C9/04—Carcasses the reinforcing cords of each carcass ply arranged in a substantially parallel relationship
  • B60C2009/0416—Physical properties or dimensions of the carcass cords
  • B60C2009/0466—Twist structures
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/04—Heat-responsive characteristics
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2505/00—Industrial
  • D10B2505/02—Reinforcing materials; Prepregs
  • D10B2505/022—Reinforcing materials; Prepregs for tyres

Definitions

• Rubberised reinforcement for elastomeric products in particular vehicle tires, the reinforcement having at least one first yarn, method for producing the rubberised reinforcement and vehicle tires having at least one rubberised reinforcement
• the invention relates to a rubberized reinforcement for elastomeric products, in particular vehicle tires, the reinforcement having at least one first yarn, a method for producing the rubberized reinforcement and a vehicle tire having at least one rubberized reinforcement.
• Reinforcements for reinforcing various elastomeric products are well known. So it is known for vehicle tires that they usually have different reinforcements in different components, which are each surrounded by a rubber mixture, also known as a rubber coating mixture. The reinforcements are thus contained as rubberized reinforcements in the vehicle tire.
• PET polyethylene terephthalate
• HMLS-PET high modulus low shrinkage polyethylene terephthalate
• HMLS-PET high modulus low shrinkage polyethylene terephthalate
• Efforts are also being made to resolve existing conflicting goals of sustainability and performance requirements when selecting the materials for elastomeric products, such as vehicle tires, or at least to achieve an improvement.
• DE 102010017107 A1 discloses a reinforcement cord which has at least one yarn made from recycled PET.
• the recycled PET can in particular come from PET beverage bottles.
• recycled PET due to its properties.
• recycled PET from bottles contains additives that impair crystallization during processing, such as in particular the spinning process into an industrial yarn.
• the physical properties are worse than traditional PET, i.e. PET that is not recycled PET but was originally produced. This is particularly important in the case of PET, which is subject to high demands in terms of shrinkage, deformability and extensibility (stretch) and strength.
• the present invention is therefore based on the object of providing a rubberized reinforcement for elastomeric products, in particular vehicle tires, the reinforcement having at least one first yarn, which has high strength and high extensibility and at the same time is produced in the most resource-saving, sustainable and environmentally friendly way possible.
• the first yarn is a yarn made of HMLS-PET, which includes recycled PET.
• the first yarn comprises 10% to 100% by weight recycled PET.
• the first yarn made of HMLS-PET comprising recycled PET, preferably 10 to 100% by weight recycled PET, is also referred to as “the first yarn” in the context of the present invention.
• a rubberized reinforcement having at least one yarn made of PET, the yarn comprising recycled PET, preferably 10 to 100% by weight, and at the same time having a high modulus and therefore high strength has low shrinkage and can therefore be classified as HMLS-PET yarn.
• the reinforcement according to the invention has the advantages that it is produced in a more resource-saving and environmentally friendly manner than original (“virgin”) PET and still meets the high requirements for properties, especially for use in elastomeric products, such as in the carcass layer of vehicle tires.
• the weight data in percent (% by weight) relate to the ungummed and unpretreated, i. H. especially undip, yarn.
• recycled PET is understood to mean PET which has been obtained from old PET products such as PET bottles or other PET articles such as clothing, for example.
• the direct starting material for recycled PET is not petroleum, but bottles or other items made from PET.
• the reinforcement comprises less than 100% by weight of recycled PET, ie for example and in particular 10 to ⁇ 100% by weight of recycled PET, the remaining proportion is original PET.
• Virgin PET which has not gone through a recycling process and comes from petroleum-based (petrochemical) or renewable raw materials.
• the price and the CCk load can be set individually in the production of the rubberized reinforcements and vehicle tires according to the invention.
• the object on which the invention is based is achieved particularly well with a higher proportion of recycled PET, but a proportion of recycled PET of, for example, 10% by weight also contributes to the conservation of resources and a lower CO2 load.
• the first yarn of HMLS-PET comprises 20 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 30 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 40 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 50 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 60 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 70 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 80 to 100% by weight recycled PET. According to advantageous embodiments, the first yarn of HMLS-PET comprises 90 to 100% by weight recycled PET.
• the first yarn of HMLS-PET comprises 100% by weight recycled PET.
• the yarn of HMLS-PET comprises 30% to 100% by weight, more preferably 50% to 100% by weight, of recycled PET.
• Recycled PET differs from original (virgin) PET in terms of additives, such as the isophthalic acid (IPA) content in particular.
• additives such as the isophthalic acid (IPA) content in particular.
• IPA isophthalic acid
• the recycled PET used in the context of the present invention it is, for example and in particular, 1.2 to 2.2% by weight.
• the weight data in percent (% by weight) relate to the PET and thus in the reinforcement according to the invention to the ungummed and unpretreated, i. H. especially undip, yarn.
• the isophthalic acid content is therefore 0.12 to 0.5% by weight, preferably 0.12 to 0.22% by weight. %.
• the first yarn made of HMLS-PET preferably has an isophthalic acid (IPA) content of 0.12 to 5% by weight, for example and preferably 0.12 to 2.2% by weight.
• IPA isophthalic acid
• An “HMLS yarn” is understood to mean a yarn that has a high modulus and low shrinkage.
• the first yarn made of HMLS-PET has a heat shrinkage of less than 8%, more preferably 4 to 8%, and an elongation at 45 N of less than 0.0056%/den (percent per denier), more preferably 0.002 to 0.0056%/denier, with filament finenesses of less than 5 denier, particularly preferably 3 to 5 denier.
• This information is particularly suitable for characterizing the first yarn made from HMLS-PET as an HMLS yarn.
• the first yarn of the inventive strength member preferably has a breaking strength of 7.0 to 9.0 g/denier (grams per denier).
• the first yarn of the reinforcement according to the invention preferably has an elongation at break of 10.2 to 15.5%.
• the first yarn is in particular and preferably an endless multifilament yarn and thus preferably not a monofilament yarn and preferably not a staple fiber yarn.
• the first yarn of the reinforcement according to the invention preferably comprises filaments with filament counts of less than 5 deniers, d. H. each filament of the yarn is preferably finer than 5 denier.
• the first yarn particularly preferably has a filament fineness of 3 to 5 deniers.
• the first yarn has an elongation at a force of 45N of less than 0.0056%/denier.
• the breaking strength, the elongation at 45 N and the elongation at break are determined using an Instron tensile tester in accordance with ASTM D885: Instron 5564 device, clamp: C- clamp, 2714-004 with pneumatic activation, loading capacity 1 kN (one kiloNewton), test conditions: gauge length 250 mm, crosshead speed 300 mm/min , preload 0.05 gf/den (gram-force per denier), air pressure 0.4 to 0.6 MPa, conditioning of samples before test: 24 hours at 24 ⁇ (plus minus) 2 °C, 55 ⁇ 5% Humidity.
• the first yarn of the reinforcement according to the invention preferably has a heat shrinkage at 177° C. of 3.2 to 5.2%.
• the heat shrinkage of yarns is determined using the hot air shrinkage method according to ASTM D885.
• the test conditions are: temperature 177°C, load 0.05g/denier, duration 10 min.
• the first yarn made of HMLS-PET preferably has a degree of crystallization of 45 to 53.5%.
• the degree of crystallization is determined according to ASTM DI 505 as follows: First, the yarn density is determined using a density gradient column. The degree of crystallization is then calculated by interpolation using the literature values given below for the density of 100% amorphous and 100% crystalline PET. The density of 100% amorphous PET is 1.333 g/cm 3 while that of 100% crystalline PET is 1.455 g/cm 3 .
• the yarn and thus the reinforcement according to the invention can be produced with such a degree of crystallization and at the same time has the necessary properties with regard to expansion and shrinkage behavior for the high requirements, in particular when used in the carcass layer of vehicle tires.
• the first yarn of HMLS-PET has a fineness of 300 to 4000 denier (denier), preferably 300 to 3100 denier, more preferably 300 to 2000 denier, most preferably 900 to 2000 denier.
• the first yarn is twisted and further processed as described below.
• the reinforcement according to the invention comprises a twisted rubberized yarn.
• one or more yarns can also be twisted to form a cord.
• a first yarn is like
• an HMLS-PET yarn is described comprising, preferably 10 to 100% by weight, recycled PET.
• the at least one further (second) yarn is also an HMLS-PET yarn comprising, preferably 10 to 100% by weight, recycled PET, so that according to this embodiment at least two of the HMLS-PET yarns described are combined to form a cord are twisted.
• the first yarn is twisted in a x2 cord, the cord having a twist factor of 150 to 250, preferably 170 to 230, and a breaking strength of at least 6.3 g/denier, preferably 6.3 to 10 g /Den, and an elongation at 45 N of less than 0.0056%/Den, preferably 0.0005 to 0.0040%/Den, and a heat shrinkage of less than 3%, preferably 1 to 3%, particularly preferably 1, 5 to 2.5%.
• x2Cord means that two yarns have been twisted together.
• a first yarn--as described according to the invention an HMLS-PET yarn comprising recycled PET--is twisted with preferably a second further HMLS-PET yarn comprising recycled PET to form a cord.
• the heat shrinkage of cords is determined by means of the hot air shrinkage method according to ASTM D885 at 180.degree.
• the test conditions are: temperature 180°C, load 0.05g/denier, duration 10 min.
• the at least one further yarn is another yarn and thus the reinforcement according to the invention is a hybrid cord comprising an HMLS-PET yarn comprising, preferably 10 to 100% by weight, recycled PET and at least one other yarn is.
• the at least one further yarn is (consists of) a non-metallic material.
• the non-metallic material is preferably selected from the group containing polyamide (PA) and/or aramid and/or polyetherketone (PEK) and/or polyketone (POK) and/or polyethylene naphthalate (PEN) and/or rayon and/or viscose and/or natural fibers and/or glass fibers.
• PA polyamide
• PEK polyetherketone
• POK polyketone
• PEN polyethylene naphthalate
• rayon and/or viscose and/or natural fibers and/or glass fibers rayon and/or viscose and/or natural fibers and/or glass fibers.
• the described yarns and/or the described cords are woven into a textile layer before this is further processed by adhesion activation and rubber coating with a rubber coating mixture.
• a further object of the present invention is a reinforcement layer made from a multiplicity of rubberized reinforcements according to the invention.
• a further object of the present invention is a vehicle tire which has at least one rubberized reinforcement according to the invention.
• the vehicle tire has a multiplicity of rubberized reinforcements according to the invention in a reinforcement layer.
• the reinforcement layer is preferably the carcass layer and/or a belt bandage and/or a belt layer and/or a bead reinforcement, particularly preferably at least the carcass layer.
• the vehicle tire according to the invention can thus also have the reinforcement according to the invention in one or more components, preferably at least in the carcass ply.
• the reinforcement layer is at least the carcass layer, with the carcass layer being guided around the bead once (single-layer construction) or twice (two-layer construction) as part of a ply turn-over, with the end of the layer or layers between core and belt edge.
• the vehicle tire is further improved in terms of its load capacity.
• the yarn is produced as a continuous multifilament yarn as described.
• Devices known to those skilled in the art are used to carry out the process steps described in more detail, unless otherwise stated.
• PET chips comprising 100% by weight recycled PET from PET bottles or other PET products
• chips made from recycled PET are also referred to herein as “chips made from recycled PET”.
• the intrinsic viscosity is determined using an Ubbelohde Capillary Viscometer in accordance with ASTM D4603.
• the yarn comprises less than 100% by weight recycled PET, i.e. in particular 10 to ⁇ 100% by weight recycled PET
• the remaining proportion is original PET (Virgin PET), which has not undergone a recycling process and comes from petroleum-based (see petrochemicals) or renewable raw materials.
• the additives present in recycled PET for example alternative monomers to »-terephthalic acid, such as IPA, for example, weaken the PET's ability to crystallize during the spinning process. This makes spinning and drawing into a yarn more difficult, and its properties are inferior to yarn made from original PET.
• step b) The pre-crystallization, crystallization and solid-state polymerization (SSP) in step b) result in further polymerization and thus a reduction in the proportion of shorter polymer molecules achieved, whereby a molecular chain growth is achieved. This results in an increased intrinsic viscosity. This improves the drawability of the material while also improving the tensile stiffness and modulus (stiffness) of the yarn.
• SSP solid-state polymerization
• the crystallization rate can be adjusted in such a way that a high spinning speed and a high draw rate can be selected during the spinning process.
• Solid-state polymerization is a process where the raw PET chips are placed in a reactor and heated to polymerize. Here, the molecular chain length and the intrinsic viscosity are increased. The intrinsic viscosity of recycled PET chips is 0.55 to 0.75 dl/g.
• solid-phase polymerisation is also referred to in German as solid-phase condensation, since condensation takes place as a result of the removal of water.
• the raw PET chips are preferably pre-crystallized for 0.5 to 1.5 hours at a temperature of 150 to 180 °C and then crystallized for 4 to 6 hours at a temperature of 200 to 230 °C and finally for 30 to 35 Reacted for hours in an SSP reactor at a wall temperature of 200-220°C.
• the entire system of devices is operated in a nitrogen atmosphere, with the oxygen content of the nitrogen being maintained at 30 to 70 ppm and the dew point preferably being lower than -70°C (lower than minus 70°C).
• step c) drying is preferably carried out under nitrogen, the drying temperature preferably being from 120 to 160° C. and the drying time preferably being more than 8 hours. This reduces the water content of the highly viscous chips to less than 30 ppm.
• the melting and extruding of the high-viscosity PET chips in step c) preferably takes place as a melt extrusion in a screw extruder, the temperature in the feed zone of the screw extruder being 300 to 330° C., the temperature in the compression zone being 290 to 320° C. and the temperature in in the metering zone (discharge zone) is 280 to 310 °C and the pressure at the extruder head is 14 to 18 MPa (megapascals). A melt is obtained from this.
• melt-extrusion can improve the melt viscosity and the fluidity of the high-viscosity chips, and further reduce the adverse effects due to the content of IPA, and thus further improve the drawability.
• the extrusion step further improves the homogeneity of the mixture of recycled and original PET.
• Spinning (in step c) is preferably carried out by means of a spinning jet, with the length/diameter ratio (L/D) of the spinneret opening being 1.2 to 3.0 according to advantageous embodiments.
• the spinneret comprises 180 to 480 openings and a yarn with 1000 to 1500 denier is obtained.
• a yarn with 300 to 4000 denier (denier), preferably 300 to 3100 denier, more preferably 300 to 2000 denier, most preferably 900 to 2000 denier, can be obtained, for example and in particular 500 denier, 2000 denier or 4000 Denier.
• the number of spinneret orifices can be greater than 480.
• a yarn having filaments with filament counts of less than 5 denier (denier) is obtained.
• a yarn with a filament fineness of 3 to 5 deniers is particularly preferably obtained.
• the gradual cooling in step c) has the purpose that the melt of the undrawn yarn is solidified.
• the stepwise cooling in step c) preferably comprises a circular quenching system following the buffer zone, with cooling air being blown into the inner ring from the outside, the blowing pressure being 15 to 50 Pa and the blowing temperature being 22 to 65°C.
• the undrawn yarn is post-heated, gradually cooled by means of a circular quench system following the buffer zone, and cooled with cooling air after melt-spinning.
• the oiling in step d) has the advantage that the cohesion of the undrawn yarn is increased and frictional forces and static electrical charges are reduced. This also facilitates the subsequent drawing process and reduces the frequency of filament and yarn breakage. Furthermore, this is also advantageous for the subsequent processing steps for the rubberized reinforcement or for the fabric layer, namely in particular for twisting and weaving, since the yarn slides better as a result of the oiling.
• the oil is preferably used in an emulsion and the oil absorption rate is preferably 0.3 to 0.9% by weight, based on the yarn.
• the drawing in step d) is preferably carried out by means of a godet roller construction, with a first pair of godet rollers (GW1) running at a speed of 2700 to 3200 m/min at a temperature of 60 to 80 °C, a second pair of godet rollers (GW2 ) at a speed of 3800 to 5000 m/min at a temperature of 70 to 90 °C and a third pair of godet rolls (GW3) at a speed of 5800 to 6200 m/min at a temperature of 210 to 260 °C and the draw rate is preferably 1.81 to 2.30%.
• GW1 godet rollers
• GW2 second pair of godet rollers
• GW3 third pair of godet rolls
• optimal properties of the yarn produced can be achieved, such as optimized breaking strength and elongation at break, as well as optimized heat shrinkage and modulus.
• the heat hardening that takes place after the drawing is preferably carried out by means of a fourth pair of godet rollers (GW4) at a speed of 5800 to 6200 m/min at a temperature of 210 to 260 °C, a subsequent fifth pair of godet rollers (GW5) at a speed of 5600 to 6200 m/min at a temperature of 210 to 260 °C and a subsequent sixth pair of godet rolls (GW6) at a speed of 5450 to 6000 m/min at a temperature of 100 to 150 °C, the relaxation rate being 2.5 to 6.0%.
• GW4 godet rollers
• GW5 a subsequent fifth pair of godet rollers
• GW6 a subsequent sixth pair of godet rolls
• the yarn is thus optimally prepared for the subsequent winding process and heat curing.
• the winding in step d) preferably takes place at a winding speed of 5450 to 5950 m/min.
• a yarn is obtained which has a breaking strength of 7.5 to 9.0 g/d, an elongation at break of 10.2 to 15.5%, a heat shrinkage of 3.2 to 5, 2%, a degree of crystallization of 45 to 53.5% and an IPA content of 0.12 to 5% by weight, in particular 0.12 to 2.2% by weight.
• the yarn having a fineness of 300 to 4000 deniers can be obtained.
• the HMLS-PET yarn obtained comprising 10 to 100% by weight recycled PET is further processed in particular and preferably by at least the following process steps in order to obtain the rubberized reinforcement according to the invention: e) twisting f) optional weaving; g) providing adhesion with a dip h) gumming with a gum mixture
• the yarn itself is first twisted and then twisted with another yarn that has also been twisted to form a cord.
• the yarns used in the cord can each be made up of filaments twisted in the S or Z direction.
• the HMLS-PET yarn comprising recycled PET may be S- or Z-twisted.
• the twisted yarns are then final twisted in the S or Z direction into a reinforcement cord.
• the yarns of a reinforcement cord all have the same twist direction, i.e. they are twisted in either the S or Z direction.
• the reinforcing cord has the opposite twisting direction to the yarns.
• an S-twisted HMLS-PET yarn comprising recycled PET can be end-twisted in the Z-direction with another S-twisted HMLS-PET yarn - comprising recycled PET - to form a reinforcement cord.
• two yarns are twisted in a direct cabling machine to form a cord made of two yarns (x2 cord).
• the number of twists of the yarns and cords (tpm, “turns per meter”) is preferably 100 to 500 tpm in each case.
• Cords comprising the first yarn preferably have a twist factor TF of 150 to 250.
• the twist factor TF is calculated as follows according to formula I):
• N the number of twists (in tpm) and K is the cord gauge and “ A 0.5” should represent the square root (from the expression in brackets), i.e
• step f When weaving (step f), the following should preferably be observed:
• the tension of each thread spool is controlled by roller bearings and rubber belts to ensure consistent tension.
• the yarn is fed through the reed, which is adjusted according to specifications, and woven on an air-jet loom. Then, the cord is woven into greige fabric having a preset width, in particular, the weft yarn is a yarn having an elastic core of, for example, PET or nylon, which is wrapped with, for example, cotton.
• step f) The gray fabric obtained in step f) is then processed further in step g) using a dip.
• the dip can include a pre-dip and an RFL dip (resorcinol-formaldehyde-latex) known in the prior art or an environmentally friendly and health-friendly RFL-free alternative, as described for example in DE 102014211362 A1 or WO 2019015792 A1.
• RFL dip resorcinol-formaldehyde-latex
• the adhesion finishing by means of a dip according to step g) can thus include, in particular, 1-bath or 2-bath processes (pre-dip and dip) known in the prior art.
• step h takes place in a manner known to those skilled in the art using a gumming mixture and devices known to those skilled in the art.
• drying is carried out at high temperatures, in particular at more than 100° C., before gumming.
• the rubber coating mixture can be any suitable rubber coating mixture for encasing reinforcements, in particular textile reinforcements, known to those skilled in the art.
• the gumming mixture preferably contains at least one diene rubber.
• the diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR) .
• the rubber mixture contains at least one carbon black as a non-polar filler.
• the carbon black is preferably used in amounts of 0.1 to 100 phr, particularly preferably in amounts of 40 to 100 phr, very particularly preferably in amounts of 40 to 80 phr, in the rubber mixture. It is again particularly preferred if the rubber mixture contains 57 to 67 phr of at least one carbon black. This achieves particularly good mixing properties with regard to tearing properties.
• the method described comprising at least steps a) to h) is a further subject of the present invention.
• the reinforcement according to the invention is preferably produced using this method.
• a further object of the present invention is thus the reinforcement obtained by means of the method described.
• Table 1 first gives an overview of yarns and their production parameters, which are used by way of example in the reinforcement according to the invention.
• Fig. 1 the examples E1 to E6 - indicated by the proportion of recycled PET - plotted in a bar chart, the height of the bars the CCk emission (kg CC /kg product).
• the information relates to the PET chip production excluding the contributions to the production of the monomers such as monoethylene glycol (MEG) and PTA (engl. "Purified Terephthalic Acid”).
• the subsequent processes starting with yarn production are considered to be independent of the PET raw material with regard to CO2 emissions.
• the bar on the left represents the CCh emission from virgin PET, while the two bars on the right represent the CCh emission from bio-based PET (the monomer ethylene glycol was derived from corn, so about 30% by weight of the raw materials come from renewable resources) and HIPS (high-impact polystyrene).
• the lowest CCh emission is achieved with a PET which is made from 100% by weight recycled PET.
• the C02 balance of the recyclate only begins after it has been used in a PET bottle, for example
• the value essentially includes shredding and remelting into PET chips.
• the properties were determined using the methods described above.
• the degree of filament breakage in the yarn manufacturing process was also included as a further criterion. For each spool (9 kg, 62 km long, 1300 denier) it was determined that the number of broken filaments had to be less than 10 in order to be classified as qualified (Q). Otherwise the sample was rated as insufficient (NQ).
• Table 2 The data in Table 2 show that yarns produced by the process according to steps a) to d) comprising the solid state polymerisation, spinning, cooling and drawing processes have properties such as breaking strength and elongation at break that are comparable to traditionally manufactured yarns.
• rubberized reinforcements according to the invention and vehicle tires having the rubberized reinforcements, in particular in a reinforcement layer can be produced efficiently and with a low waste rate ( ⁇ 4%), with the corresponding requirements being met at the same time due to the high-quality properties care is taken when using it.
• the homogeneity of the viscosity, the melting point and the crystallization rate of the high-viscosity chips can be effectively controlled.
• Example V4 shows that if the after-heating and buffer zone after spinning is omitted, the undrawn yarn cools too quickly and hardens and crystallizes prematurely, which leads to lower production efficiency and poorer physical properties.
• Example V5 shows that in the case of omitting the pre-crystallization and the crystallization in the SSP process and omitting the post-heating and buffer zone after spinning, poor homogeneity of the high-viscosity chips and a fast crystallization rate during spinning and poorer spinnability and a lower degree of crystallization of the finished yarn can be achieved.
• the pre-crystallization and the crystallization should be combined with the post-heating and the buffer zone as described above to slow down the crystallization rate and increase the degree of crystallization.
• Cords were produced from the yarns of Examples E1 to E6 and V2 to V5 listed above by twisting two yarns each, these were woven and dipped, with the result that a dipped fabric was obtained.
• the yarns have been twisted in the S direction while the cord has been twisted in the Z direction.
• the tension of each thread spool was controlled by roller bearings and rubber belts to ensure consistent tension.
• the yarn was passed through the reed, adjusted to specifications, and woven on an air-jet loom. Then the cord was woven into greige fabric with a preset width, the weft yarn being a 22.2 tex nylon core-spun yarn (core made of nylon monofilament, covered with staple fibers made of cotton, engl "core spun yarn").
• the raw fabric obtained was then further processed using a dip.
• a 2-bath immersion method was used here.
• An epoxy compound (trade name Grilbond® G 1701, EMS-GRILTECH) and an isocyanate compound (trade name Grilbond® IL-6 50% F, EMS-GRILTECH) were provided in a first bath and the yarns were dipped therein and thus their superficial filaments activated.
• a resorcinol-formaldehyde latex (precondensed resin of resorcinol and formaldehyde in an aqueous dispersion mixed with formaldehyde and latex, among other things) was provided in a second bath and the tissue activated by the first bath was dipped in it.
• Hot stretching also took place, with a net stretching of 0 to 1% being set.
• the specification 1500/2 is to be understood as 1500 Den /2 and means that 2 games, each with a fineness of 1500 Denier, were twisted into one cord. The same applies to the specification 1000/2.
• Residual strength was determined using a Goodrich fatigue test under the following conditions: 1800 rpm (revolutions per minute), duration 24 hours, 20% compression, 6.5% tension, at room temperature. Table 3
• examples E1 to E6 made it possible to produce cords whose properties meet the requirements for use in a rubberized reinforcement according to the invention, in particular for vehicle tires.
• the comparative examples C2 to C5, on the other hand, show poorer properties and are therefore not so well suited.
• the greater damage to the filaments during high-speed spinning means that the fatigue resistance of the cords produced is greatly adversely affected.
• example V2 the sample broke before the end of the fatigue test.
• the vehicle tire according to the invention has the rubberized reinforcement at least in the carcass ply, specifically in particular a large number of the rubberized reinforcements in a corresponding reinforcement ply that forms the carcass ply.
• Table 4 shows an exemplary composition of a rubber mixture for the rubberized reinforcement according to the invention.

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• 2020
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